CN102260221A - Preparation method of isocyanurate acrylate or isocyanurate methacrylate monomer - Google Patents
Preparation method of isocyanurate acrylate or isocyanurate methacrylate monomer Download PDFInfo
- Publication number
- CN102260221A CN102260221A CN2011101503273A CN201110150327A CN102260221A CN 102260221 A CN102260221 A CN 102260221A CN 2011101503273 A CN2011101503273 A CN 2011101503273A CN 201110150327 A CN201110150327 A CN 201110150327A CN 102260221 A CN102260221 A CN 102260221A
- Authority
- CN
- China
- Prior art keywords
- isocyanuric acid
- acrylate
- methacrylate monomer
- hydroxyethyl
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 0 CN(C(N(C)C(N1*)=O)=O)C1=O Chemical compound CN(C(N(C)C(N1*)=O)=O)C1=O 0.000 description 3
Images
Abstract
The invention discloses a preparation method of isocyanurate acrylate or isocyanurate methacrylate monomer. The preparation method comprises the following steps: carrying out esterification reaction on different molar ratios of tris(2-hydroxyethyl) isocyanurate and acrylic acid or methacrylic acid in the presence of a catalyst and a water carrying agent, and carrying out a series of purification and separation processes on the synthesis products to obtain triazine-ring-containing bifunctional and trifunctional isocyanurate acrylate or isocyanurate methacrylate monomer. The multifunctional monomer obtained by the preparation method has the maximum esterification rate up to 94% or above and the yield up to 91% or above. Because of containing a rigid triazine ring structure in the molecule, the synthesized multifunctional monomer has the advantages of no significant volume contraction of coating film after ultraviolet (UV) curing, pencil hardness up to 6H or above, water absorption rate as low as 0.5-1.0% and oil absorption rate as low as 2.5% or below, is an excellent UV resin modifier and cross-linking monomer, and is widely used in the fields of radiation-curable coatings, adhesives and ink.
Description
Technical field
The present invention relates to the preparation method of a kind of isocyanuric acid acrylate or isocyanuric acid methacrylate monomer, particularly relate to a kind of polyfunctionality isocyanuric acid acrylate of triazine ring or preparation method of isocyanuric acid methacrylate monomer of containing.
Background technology
UV-light (UV) curing technology is because it is efficient, environmental protection and save energy and be widely used in a plurality of fields such as paint, coating, printing ink and tackiness agent.Along with the concern of people to environment, the formulation and the enforcement of restriction and minimizing volatile organic matter (VOC) Abgasgesetz, ultraviolet-curing paint (UV coating) replaces traditional solvent based coating just gradually.
The general prescription of UV coating comprises photosensitive prepolymer, activity diluting monomer and light trigger, wherein activity diluting monomer and photosensitive prepolymer are mainly acrylate monomer and all kinds of acrylic ester prepolymer that contains unsaturated double-bond, as epoxy acrylate, urethane acrylate, polyester acrylate etc.Acrylate monomer is broadly divided into general acrylate monomer and extraordinary acrylate monomer by its structure.Extraordinary acrylate monomer is meant the acrylate monomer that those have special construction or contain specific functional groups, its functional group can be the ester group of different carbon chain lengths, also can contain special elementses such as special constructions such as amino, hydroxyl, epoxy group(ing), furan nucleus, triazine ring and phosphorus, silicon, fluorine etc., thereby be a kind of highly active comonomer, both polymer raw material can be made, active solvent or diluent, linking agent etc. can be made again.Contain the hexa-atomic carbon nitrogen heterocyclic of stable rigidity (triazine ring) structure in three (2-hydroxyethyl) isocyanuric acid esters (THEIC), have excellent chemistry and thermostability.If utilize the reactive behavior that has 3 active hydroxyls in its molecule that it is incorporated on the photosensitive film-forming resin main chain, can improve intensity, thermotolerance, weathering resistance and the flame retardant resistance of UV coating.Simultaneously, owing on the triazine ring in the molecule three functional groups are arranged, and structure is huge, and molecular chain is piled up lax, can be used for the star-like or branch type polymkeric substance of the synthetic high degree of branching, and then prepares the UV coating of low viscosity, high solids content.Therefore, through (methyl) acroleic acid esterification and isocyanuric acid (methyl) acrylate monomer be the extraordinary acrylate monomer of the splendid polyfunctionality of a kind of performance.About the research of such extraordinary monomeric synthetic and application facet, domesticly do not see bibliographical information.
Esterification is a sulfuric acid at the industrial catalyzer of continuing to use always, but sulfuric acid has the effect of esterification and oxidation concurrently, esterification takes place in, be attended by the generation of side reaction in the system, this can make the rectifying of reaction product and recovery add to the difficulties, and extremely strong to the corrodibility of equipment, therefore, sulfuric acid is replaced by the catalyzer of other types gradually at present, as TiO
2/ SO
4 2-Solid super-strong acid, strongly acidic cation-exchange and tosic acid.Yet, in the catalysis that contains the isocyanuric acid of triazine ring structure (methyl) acrylate monomer is synthetic, experimental results show that the esterification effect of tosic acid is best.This is because tosic acid also is a kind of strong organic acid, and is identical with the catalytic mechanism of the vitriol oil; Simultaneously, compare with the vitriol oil, tosic acid can not produce other side reactions and severe corrosive because of there not being oxidisability.And in contrast, strongly acidic cation-exchange and solid super-strong acid then almost do not have katalysis, and this is because the ring-type macromolecular structure of THEIC has bigger sterically hinderedly, is difficult to carry out effective esterification under the heterogeneous catalysis system effect.
Summary of the invention
The object of the invention is to utilize wide material sources, three (2-hydroxyethyl) isocyanuric acid esters (THEIC) with low cost as a kind of polyol, carry out the modification of acrylic or methacrylic acid esters, so that a kind of good polyfunctionality isocyanuric acid acrylate of triazine ring, curing performance or preparation method of isocyanuric acid methacrylate monomer of containing to be provided.
Purpose of the present invention is achieved through the following technical solutions:
The preparation method of difunctionality isocyanuric acid acrylate or isocyanuric acid methacrylate monomer comprises the steps:
(1) the elementary product of monomer is synthetic: acrylic or methacrylic acid, three (2-hydroxyethyl) isocyanuric acid ester, band aqua, stopper and catalyzer are mixed, the oil bath heating, after the question response thing all dissolves, control reaction temperature is 100～120 ℃, carry out the esterification dehydration, generate, the cooling stopped reaction until reactionless water, decompression removes the band aqua, obtains containing the difunctionality isocyanuric acid acrylate of triazine ring or the elementary product of isocyanuric acid methacrylate monomer; The mol ratio of described three (2-hydroxyethyl) isocyanuric acid esters and acrylic or methacrylic acid is 1: (2.7～3.6); Described catalyzer is a tosic acid, and consumption is 7.5%～10.0% of three (2-hydroxyethyl) isocyanuric acid ester quality; Described stopper is MEHQ or 2, and 6-Butylated Hydroxytoluene, consumption are 6%～8% of acrylic or methacrylic acid quality; Described band aqua is hexanaphthene and/or toluene, and consumption is 100%～140% of three (2-hydroxyethyl) isocyanuric acid ester quality;
(2) purify: step (1) reaction system is cooled to below 50 ℃, adds Na
2CO
3Solution is regulated PH=7.5～8, and is stirred well to no bubble generation, makes system be neutral with the saturated common salt water washing again; Use deionized water wash at last 3～5 times,, obtain colourless or little yellow transparent liquid through the vacuum decompression drying;
(3) separation and purification: with the purified product acetic acid ethyl dissolution of step (2), the insolubles precipitation is separated out, removed solvent, obtain difunctionality isocyanuric acid acrylate or isocyanuric acid methacrylate monomer through underpressure distillation with centrifuging.
Further, the mol ratio of described three (2-hydroxyethyl) isocyanuric acid esters and acrylic or methacrylic acid is preferably 1: (3.0～3.3).
The time of described esterification dehydration is preferably 5～6 hours.
Described step (2) Na
2CO
3Solution quality concentration is preferably 10%～15%; Preferred 2～3 times of saturated common salt water washing.
The insolubles of described step (3) is an isocyanuric acid mono acrylic ester insolubles.
The preparation method of three-functionality-degree isocyanuric acid acrylate or isocyanuric acid methacrylate monomer comprises the steps:
(1) the elementary product of monomer is synthetic: acrylic or methacrylic acid, three (2-hydroxyethyl) isocyanuric acid ester, band aqua, stopper and catalyzer are mixed, the oil bath heating, after the question response thing all dissolves, control reaction temperature is 100～120 ℃, carrying out the esterification dehydration generates until reactionless water, the cooling stopped reaction, decompression removes the band aqua, obtains containing the three-functionality-degree isocyanuric acid acrylate of triazine ring or the elementary product of isocyanuric acid methacrylate monomer; The mol ratio of described three (2-hydroxyethyl) isocyanuric acid esters and acrylic or methacrylic acid is 1: (5.5～8.0); Described catalyzer is a tosic acid, and consumption is 7.5%～10% of three (2-hydroxyethyl) isocyanuric acid ester quality; Described stopper is MEHQ or 2, and 6-Butylated Hydroxytoluene, consumption are 6%～8% of acrylic or methacrylic acid quality; Described band aqua is hexanaphthene and/or toluene, and consumption is 100%～140% of three (2-hydroxyethyl) isocyanuric acid ester quality;
(2) purify: step (1) reaction system is cooled to below 50 ℃, adds Na
2CO
3Solution is neutralized to PH=7.5～8, and is stirred well to no bubble generation, uses the saturated common salt water washing again, makes system be neutral; Spend dried up washing 3～5 times at last,, obtain white paste solid through the vacuum decompression drying;
(3) separation and purification: with mixed solvent (mass ratio is 1: (0.1～the 0.2)) dissolving of the purified product of step (2) with ethyl acetate and hexanaphthene, with centrifuging the insolubles precipitation is separated out, remove solvent through underpressure distillation, obtain three-functionality-degree isocyanuric acid acrylate or isocyanuric acid methacrylate monomer.
Further, the time of described esterification dehydration is preferably 5～6 hours.
Described step (2) Na
2CO
3Solution quality concentration is preferably 10%～15%; Preferred 2～3 times of saturated common salt water washing.
The insolubles of described step (3) is isocyanuric acid mono acrylic ester and isocyanuric acid double methacrylate insolubles.
Esterification yield of the present invention calculates and gets according to the per-cent of the actual aquifer yield of partial esterification with the theoretical aquifer yield of complete esterification, wherein the theoretical esterification yield of difunctionality isocyanuric acid acrylate or isocyanuric acid methacrylate monomer is 66.7%, and the theoretical esterification yield of three-functionality-degree isocyanuric acid acrylate or isocyanuric acid methacrylate monomer is 100%.The Mass Interference of a small amount of acrylic or methacrylic acid of taking out of when crystal water of introducing in the calculating palpus eliminating catalyzer of esterification yield and solvent refluxing.The highest esterification yield of polyfunctionality isocyanuric acid acrylate or isocyanuric acid methacrylate monomer can reach more than 94%, and the monomer yield after purified can reach more than 91%.
Described polyfunctionality isocyanuric acid acrylate or isocyanuric acid methacrylate monomer have the uV curable characteristic, and cured product has excellent mechanical property and water-fast, oil-proofness.
Preparation method of the present invention adopts benzene methanesulfonic acid is made catalyzer, the mixture of hexanaphthene and toluene is made the band aqua, part or all of esterification is carried out in three (2-hydroxyethyl) isocyanuric acid esters (THEIC) and acrylic or methacrylic acid, and elementary product carried out series of separate and purifying technique, thereby obtain containing the polyfunctionality isocyanuric acid acrylate or the isocyanuric acid methacrylate monomer of triazine ring.Because the THEIC wide material sources, with low cost, acrylic or methacrylic acid waits other raw materials also cheap and easy to get, and therefore the isocyanuric acid acrylate or the isocyanuric acid methacrylate monomer raw materials cost of preparation are lower, and bigger cost advantage is arranged.
Compare with the synthetic technology of existing polyfunctional acrylic ester monomer, the present invention has following advantage:
(1) the present invention adopts wide material sources, with low cost and three (2-hydroxyethyl) isocyanuric acid esters (THEIC) that contain triazine ring as polyol, carry out part or all of esterification with acrylic or methacrylic acid, can obtain the polyfunctionality isocyanuric acid acrylate or the isocyanuric acid methacrylate monomer of carbon containing nitrogen heterocyclic (triazine ring) structure, with this as UV coating material solidified and other radiation curing product activity monomers, linking agent or properties-correcting agent, have incomparable performance advantage of existing polyfunctional acrylic ester monomer and cost advantage.
(2) the present invention adopts the catalyzer of tosic acid as esterification, has avoided the strong oxidizing property of concentrated sulfuric acid catalyst and the harm that severe corrosive brings, and the highest esterification yield can reach more than 94%, and the final product yield can reach more than 91%.
(3) the polyfunctionality isocyanuric acid acrylate or the isocyanuric acid methacrylate monomer of the present invention's preparation have very high hardness of film and water-fast solvent resistance behind ultraviolet light polymerization.With difunctionality isocyanuric acid acrylate monomer is example, and its UV cured film pencil hardness is greater than 6H, and water-intake rate is low to moderate 0.5%～1.0%, and oil absorbency is low to moderate below 2.5%, and does not have obvious volumetric shrinkage.By comparison, the UV cured film hardness of common three-functionality-degree monomer pentaerythritol triacrylate and difunctionality monomer tripropylene glycol diacrylate then is respectively 5H～6H and 2H～4H, water-intake rate is respectively 4.0% and 1.0%, and oil absorbency then is respectively 1.6% and 12.3%.
(4) because of containing stable especially triazine ring structure in the molecular structure, use mechanical strength, thermotolerance, chemical proofing and the weathering resistance of the monomeric UV coating of this special type with giving, and have certain flame retardant resistance and radiation hardness characteristic with excellence; Simultaneously, this special type monomer has three functional groups, and structure is huge, and molecular chain is piled up lax, also can be used for the star-like or branch type polymkeric substance of the synthetic high degree of branching, and then prepares the UV coating of low viscosity, high solids content.Therefore, the polyfunctionality isocyanuric acid acrylate or the isocyanuric acid methacrylate monomer of the present invention's preparation both can have been done UV coating or other radiation curing product activity diluting monomer and linking agent, can also be as extraordinary photosensitive prepolymer synthetic properties-correcting agent, in the UV cured resin, to introduce triazine ring structure, give its excellent physical and mechanical performance.
(5) gained difunctionality monomer of the present invention is colourless or little yellow transparent liquid of 1000～1500mPa.s viscosity, and the three-functionality-degree monomer is white paste solid, and both all dissolve in organic solvents such as ethyl acetate, ethanol.
Advantage such as (6) preparation method of the present invention has that technology is simple and convenient, environmental friendliness, film quality height, application prospect are extensive is new generation of green environment-friendly and high-performance Chemicals.
Description of drawings
Fig. 1 is the FT-IR spectrogram of embodiment 1 difunctionality isocyanuric acid acrylate monomer.
Fig. 2 is the LC/MS spectrogram of embodiment 1 difunctionality isocyanuric acid acrylate monomer.
Specific implementation method
The present invention is further illustrated below in conjunction with embodiment, but embodiment does not constitute the restriction to the claimed scope of the present invention.
Embodiment 1
(1) in the reactor that thermometer, water trap, prolong and dropping funnel are housed, adds 30.0g vinylformic acid (AA), 30.0g three (2-hydroxyethyl) isocyanuric acid ester (THEIC), 30.0g band aqua hexanaphthene, 1.8g stopper 2 successively, 6-Butylated Hydroxytoluene and 3.0g catalyzer tosic acid, start and mix, and start the oil bath heating.After the question response thing all dissolved, control reaction temperature was carried out esterification dehydration 5 hours at 100～102 ℃, and to reactionless water generation, esterification yield reaches 65.4%, near the monomeric theoretical esterification yield 66.7% of difunctionality.The cooling stopped reaction, decompression removes the band aqua, obtains the elementary product of difunctionality isocyanuric acid acrylate monomer.
Three (2-hydroxyethyl) isocyanuric acid esters (THEIC) are 1: 3.6 with acrylic acid mol ratio; Catalyst levels is 10.0% of three (2-hydroxyethyl) isocyanuric acid ester (THEIC) quality; The stopper consumption is 6.0% of a vinylformic acid quality; Band aqua consumption is 100% of three (2-hydroxyethyl) isocyanuric acid ester (THEIC) quality.
Judge that according to the big I of esterification yield this elementary product is mainly difunctionality isocyanuric acid acrylate monomer, and contain vinylformic acid and the catalyzer and the stopper of a small amount of isocyanuric acid acrylic monoester thing, participation reaction.
(2) step (1) reaction system is cooled to below 50 ℃, adding 18.0g mass concentration is 10% Na
2CO
3Solution carries out acid-base neutralisation to PH=8.0, and is stirred well to no bubble generation, leaves standstill after 5 minutes and removes water layer; Make it to be neutral for 3 times with isopyknic saturated common salt water washing again; Spend dried up washing 3 times at last,, obtain colourless transparent liquid through the vacuum decompression drying.
(3) with an amount of acetic acid ethyl dissolution of purified product of step (2), with centrifuging a spot of isocyanuric acid acrylic monoester thing insolubles precipitation is separated out, at last the acetic acid ethyl dissolution product is removed solvent through underpressure distillation, obtain the difunctionality isocyanuric acid acrylate monomer of purifying.Through the rotational viscosimeter test, the monomeric viscosity of this purifying is 1070mPa.s as can be known.According to the variation of product quality before and after the purifying, learn that the monomeric productive rate of this purifying is 91.2%.
This purifying monomer is carried out infrared spectra (FT-IR) analysis, the results are shown in Figure 1.As seen from Figure 1, the absorption peak among the figure can be divided into two groups, and one group relevant with acryl, and another group is relevant with the THEIC structure.The absorption peak relevant with acryl has: C=C key stretching vibration absorption peak (1632cm
-1), the flexural vibration absorption peak (3033cm of unsaturated c h bond
-1, 1410cm
-1, 988cm
-1, 811cm
-1) and the vibration absorption peak (1730cm of the two keys of C=O
-1).3549cm
-1Near the absorption peak that occurs is nonesterified monohydroxy peak in the THEIC molecule.1461cm
-1, 763cm
-1The place is the charateristic avsorption band of triazine ring, 1692cm
-1The place is the absorption peak of C=O on the triazine ring.
This purification of samples is carried out liquid chromatography/mass spectrometry (LC/MS) analysis, the results are shown in Figure 2.Main mass spectra peak 170,324 and 338 among Fig. 2, corresponding respectively following molecular structure:
The interval fragment of each main mass spectra peak also comprises among Fig. 2 :-CH
2-(14);-CH
2-CH
2-OH (45);-OH (18);-CO-CH=CH
2(55);-O-CO-CH=CH
2(71) etc.
Can infer that by Fig. 1 and Fig. 2 this purified product is a difunctionality isocyanuric acid acrylate monomer (ICDA), its reaction structure formula is as follows:
The difunctionality isocyanuric acid acrylate monomer and the light trigger 1173 of purifying are mixed according to a certain percentage, be applied to slide, be cured film forming with the UV curing machine of 2KW.Cured film is through pencil hardness instrument test, and its pencil hardness is 6H, and the surface is not clamminess, and does not ftracture the finger pressure no marking.
Cured film is soaked behind the 24h all no change (nondiscoloration, non-foaming, do not come off) in 25 ℃ distilled water and ethyl acetate, calculate through weighting method, and recording its water-intake rate is 0.97%, and oil absorbency is 1.32%.
Table 1 has shown the UV curing membrane performance contrast of the difunctionality monomer of purifying and common pentaerythritol triacrylate (three-functionality-degree monomer) and tripropylene glycol diacrylate (difunctionality monomer).The result shows: because difunctionality isocyanuric acid acrylate monomer contains the inflexible triazine ring structure, its cured film hardness is apparently higher than the tripropylene glycol diacrylate cured film, suitable with the pentaerythritol triacrylate cured film, and the no obvious volumetric shrinkage in UV curing back, have excellent in water resistance and solvent resistance.
The physical and chemical performance of table 1 different monomers cured film
The structure analysis method of other embodiments of the invention gained purified product is identical with embodiment 1, and relevant spectrogram can not provide one by one with reference to figure 1 and Fig. 2.
(1) in the reactor that thermometer, water trap, prolong and dropping funnel are housed, adds 27.3g vinylformic acid (AA), 30.0g three (2-hydroxyethyl) isocyanuric acid ester (THEIC), 42.0g band aqua hexanaphthene, 1.9g stopper 2 successively, 6-Butylated Hydroxytoluene and 2.7g catalyzer tosic acid, start and mix, and start the oil bath heating.After the question response thing all dissolved, control reaction temperature was carried out esterification dehydration 5 hours at 104～106 ℃, and to reactionless water generation, esterification yield reaches 66.2%, near the monomeric theoretical esterification yield 66.7% of difunctionality.The cooling stopped reaction, decompression removes the band aqua, obtains the elementary product of difunctionality isocyanuric acid ester acrylate monomer.
Three (2-hydroxyethyl) isocyanuric acid esters (THEIC) are 1: 3.3 with acrylic acid mol ratio; Catalyst levels is 9.0% of three (2-hydroxyethyl) isocyanuric acid ester (THEIC) quality; The stopper consumption is 7.0% of a vinylformic acid quality; Band aqua consumption is 140% of three (2-hydroxyethyl) isocyanuric acid ester (THEIC) quality.
(2) step (1) reaction system is cooled to below 50 ℃, adding 16.0g mass concentration is 10% Na
2CO
3Solution carries out acid-base neutralisation to PH=8.0, and is stirred well to no bubble generation, leaves standstill after 5 minutes and removes water layer; Make it to be neutral for 2 times with isopyknic saturated common salt water washing again; Spend dried up washing 3 times at last,, obtain colourless transparent liquid through the vacuum decompression drying.
(3) with an amount of acetic acid ethyl dissolution of purified product of step (2), with centrifuging a spot of isocyanuric acid acrylic monoester thing insolubles precipitation is separated out, at last the acetic acid ethyl dissolution product is removed solvent through underpressure distillation, obtain the difunctionality isocyanuric acid acrylate monomer of purifying.Through the rotational viscosimeter test, the monomeric viscosity of this purifying is 1140mPa.s as can be known, according to the variation of product quality before and after the purifying, learns that the monomeric productive rate of this purifying is 91.8%.
This purifying monomer carries out UV film-forming and performance test according to the working method of embodiment (1), and the result shows: the pencil hardness of UV cured film is 6H, is not clamminess in the surface, does not ftracture the finger pressure no marking; Cured film is soaked behind the 24h all no change (nondiscoloration, non-foaming, do not come off) in 25 ℃ of distilled water and ethyl acetate, water-intake rate is 0.85%, and oil absorbency is 1.52%.
Embodiment 3
(1) in the reactor that thermometer, water trap, prolong and dropping funnel are housed, adds 27.3g vinylformic acid, 30.0g three (2-hydroxyethyl) isocyanuric acid ester (THEIC), 42.0g successively and be with aqua (21g hexanaphthene+21g toluene), 2.2g stopper MEHQ and 2.3g catalyzer tosic acid, start and mix, and start the oil bath heating.After the question response thing all dissolved, control reaction temperature was carried out esterification dehydration 6 hours at 113～115 ℃, and to reactionless water generation, esterification yield reaches 71.3%, a little more than the monomeric theoretical esterification yield 66.7% of difunctionality.The cooling stopped reaction, decompression removes the band aqua, obtains the elementary product of difunctionality isocyanuric acid ester acrylate monomer.
Three (2-hydroxyethyl) isocyanuric acid esters (THEIC) are 1: 3.3 with acrylic acid mol ratio; Catalyst levels is 7.5% of three (2-hydroxyethyl) isocyanuric acid ester (THEIC) quality; The stopper consumption is 8.0% of a vinylformic acid quality; Band aqua consumption is 140% of three (2-hydroxyethyl) isocyanuric acid ester (THEIC) quality, and the mass ratio of hexanaphthene and toluene is 1: 1 in the band aqua.
(2) step (1) reaction system is cooled to below 50 ℃, adding 16.0g mass concentration is 10% Na
2CO
3Solution carries out acid-base neutralisation to PH=8.0, and is stirred well to no bubble generation, leaves standstill after 5 minutes and removes water layer; Make it to be neutral for 3 times with isopyknic saturated common salt water washing again; Spend dried up washing 5 times at last,, obtain little yellow transparent liquid through the vacuum decompression drying.
(3) with an amount of acetic acid ethyl dissolution of purified product of step (2), with centrifuging a spot of isocyanuric acid acrylic monoester thing insolubles precipitation is separated out, at last the acetic acid ethyl dissolution product is removed solvent through underpressure distillation, obtain the difunctionality isocyanuric acid acrylate monomer of purifying.Through the rotational viscosimeter test, the monomeric viscosity of this purifying is 1320mPa.s as can be known, according to the variation of product quality before and after the purifying, learns that the monomeric productive rate of this purifying is 91.3%.
The pencil hardness that this purifying monomer is filmed after UV solidifies is 6H, and not being clamminess in the surface, does not ftracture the finger pressure no marking; Cured film is soaked behind the 24h all no change (nondiscoloration, non-foaming, do not come off) in 25 ℃ of distilled water and ethyl acetate, water-intake rate is 0.62%, and oil absorbency is 1.88%.
(1) in the reactor that thermometer, water trap, prolong and dropping funnel are housed, adds 27.3g vinylformic acid, 30.0g three (2-hydroxyethyl) isocyanuric acid ester (THEIC), 42.0g successively and be with aqua (28g hexanaphthene+14g toluene), 2.2g stopper MEHQ and 2.3g catalyzer tosic acid, start and mix, and start the oil bath heating.After the question response thing all dissolved, control reaction temperature was carried out esterification dehydration 6 hours at 110～112 ℃, and to reactionless water generation, esterification yield reaches 68.0%, near the monomeric theoretical esterification yield 66.7% of difunctionality.The cooling stopped reaction, decompression removes the band aqua, obtains the elementary product of difunctionality isocyanuric acid ester acrylate monomer.
Three (2-hydroxyethyl) isocyanuric acid esters (THEIC) are 1: 3.3 with acrylic acid mol ratio; Catalyst levels is 7.5% of three (2-hydroxyethyl) isocyanuric acid ester (THEIC) quality; The stopper consumption is 8.0% of a vinylformic acid quality; Band aqua consumption is 140% of three (2-hydroxyethyl) isocyanuric acid ester (THEIC) quality, and the mass ratio of hexanaphthene and toluene is 2: 1 in the band aqua.
(2) step (1) reaction system is cooled to below 50 ℃, adding 16.0g mass concentration is 10% Na
2CO
3Solution carries out acid-base neutralisation to PH=8.0, and is stirred well to no bubble generation, leaves standstill after 5 minutes and removes water layer; Make it to be neutral for 2 times with isopyknic saturated common salt water washing again; Spend dried up washing 3 times at last,, obtain little yellow transparent liquid through the vacuum decompression drying.
(3) with an amount of acetic acid ethyl dissolution of purified product of step (2), with centrifuging a spot of isocyanuric acid acrylic monoester thing insolubles precipitation is separated out, at last the acetic acid ethyl dissolution product is removed solvent through underpressure distillation, obtain the difunctionality isocyanuric acid acrylate monomer of purifying.Through the rotational viscosimeter test, the monomeric viscosity of this purifying is 1190mPa.s as can be known, according to the variation of product quality before and after the purifying, learns that the monomeric productive rate of this purifying is 92.5%.
The pencil hardness that this purifying monomer is filmed after UV solidifies is 6H, and not being clamminess in the surface, does not ftracture the finger pressure no marking; Cured film is soaked behind the 24h all no change (nondiscoloration, non-foaming, do not come off) in 25 ℃ of distilled water and ethyl acetate, water-intake rate is 0.77%, and oil absorbency is 1.74%.
Embodiment 5
(1) in the reactor that thermometer, water trap, prolong and dropping funnel are housed, adds 40.0g vinylformic acid, 20.0g three (2-hydroxyethyl) isocyanuric acid ester (THEIC), 24.0g successively and be with aqua (16g hexanaphthene+8g toluene), 3.2g stopper MEHQ and 2.0g catalyzer tosic acid, start and mix, and start the oil bath heating.After the question response thing all dissolved, control reaction temperature was carried out esterification dehydration 6 hours at 110～112 ℃, and to reactionless water generation, esterification yield reaches 94.5%, near the monomeric theoretical esterification yield 100% of three-functionality-degree.The cooling stopped reaction, decompression removes the band aqua, obtains the elementary product of three-functionality-degree isocyanuric acid ester acrylate monomer.
Three (2-hydroxyethyl) isocyanuric acid esters (THEIC) are 1: 7.2 with acrylic acid mol ratio; Catalyst levels is 10.0% of three (2-hydroxyethyl) isocyanuric acid ester (THEIC) quality; The stopper consumption is 8.0% of a vinylformic acid quality; Band aqua consumption is 120% of three (2-hydroxyethyl) isocyanuric acid ester (THEIC) quality, and the mass ratio of hexanaphthene and toluene is 2: 1 in the band aqua.
(2) step (1) reaction system is cooled to below 50 ℃, adding 15.0g mass concentration is 15% Na
2CO
3Solution carries out acid-base neutralisation to PH=7.5, and is stirred well to no bubble generation, leaves standstill after 5 minutes and removes water layer; Make it to be neutral for 3 times with isopyknic saturated common salt water washing again; Spend dried up washing 5 times at last,, obtain white paste solid through the vacuum decompression drying.
(3) with mixed solvent (mass ratio is 1: the 0.1) dissolving of the purified product of step (2) with ethyl acetate and hexanaphthene, with centrifuging a spot of isocyanuric acid acrylic monoester thing insolubles precipitation is separated out, at last the acetic acid ethyl dissolution product is removed solvent through underpressure distillation, obtain the three-functionality-degree isocyanuric acid acrylate monomer of purifying.According to the variation of product quality before and after the purifying, learn that the monomeric productive rate of this purifying is 93.2%.
The pencil hardness that this purifying monomer is filmed after UV solidifies is greater than 6H, and not being clamminess in the surface, does not ftracture the finger pressure no marking; Cured film is soaked behind the 24h all no change (nondiscoloration, non-foaming, do not come off) in 25 ℃ of distilled water and ethyl acetate, water-intake rate is 0.58%, and oil absorbency is 2.13%.
Basic identical with embodiment (4) reaction process.Wherein, the 27.3g vinylformic acid in the step (1) is used the 30.0g methacrylic acid instead, and promptly three (2-hydroxyethyl) isocyanuric acid esters (THEIC) are 1: 3.0 with the mol ratio of methacrylic acid, and the corresponding proportioning of other raw materials remains unchanged, and consumption is adjusted accordingly.The difunctionality isocyanuric acid methacrylate monomer that obtains through serial purifying technique is little yellow transparent liquid, and viscosity is 1470mPa.s, and productive rate is 91.6%.
The pencil hardness that this purifying monomer is filmed after UV solidifies is greater than 6H, and not being clamminess in the surface, does not ftracture the finger pressure no marking; Cured film is soaked behind the 24h all no change (nondiscoloration, non-foaming, do not come off) in 25 ℃ of distilled water and ethyl acetate, water-intake rate is 0.86%, and oil absorbency is 1.27%.
Embodiment 7
Basic identical with embodiment (5) reaction process.Wherein, the 40.0g vinylformic acid in the step (1) is used the 42.8g methacrylic acid instead, and promptly three (2-hydroxyethyl) isocyanuric acid esters (THEIC) are 1: 6.5 with the mol ratio of methacrylic acid, and the corresponding proportioning of other raw materials remains unchanged, and consumption is adjusted accordingly.The three-functionality-degree isocyanuric acid methacrylate monomer that obtains through serial purifying technique is white paste solid, and productive rate is 91.9%.
The pencil hardness that this purifying monomer is filmed after UV solidifies is greater than 6H, and not being clamminess in the surface, does not ftracture the finger pressure no marking; Cured film is soaked behind the 24h all no change (nondiscoloration, non-foaming, do not come off) in 25 ℃ of distilled water and ethyl acetate, water-intake rate is 0.94%, and oil absorbency is 1.13%.
Claims (9)
1. the preparation method of difunctionality isocyanuric acid acrylate or isocyanuric acid methacrylate monomer is characterized in that comprising the steps:
(1) the elementary product of monomer is synthetic: acrylic or methacrylic acid, three (2-hydroxyethyl) isocyanuric acid ester, band aqua, stopper and catalyzer are mixed, the oil bath heating, after the question response thing all dissolves, control reaction temperature is 100～120 ℃, carry out the esterification dehydration, generate, the cooling stopped reaction until reactionless water, decompression removes the band aqua, obtains containing the difunctionality isocyanuric acid acrylate of triazine ring or the elementary product of isocyanuric acid methacrylate monomer; The mol ratio of described three (2-hydroxyethyl) isocyanuric acid esters and acrylic or methacrylic acid is 1: (2.7～3.6); Described catalyzer is a tosic acid, and consumption is 7.5%～10.0% of three (2-hydroxyethyl) isocyanuric acid ester quality; Described stopper is MEHQ or 2, and 6-Butylated Hydroxytoluene, consumption are 6%～8% of acrylic or methacrylic acid quality; Described band aqua is hexanaphthene and/or toluene, and consumption is 100%～140% of three (2-hydroxyethyl) isocyanuric acid ester quality;
(2) purify: step (1) reaction system is cooled to below 50 ℃, adds Na
2CO
3Solution is regulated PH=7.5～8, and is stirred well to no bubble generation, makes system be neutral with the saturated common salt water washing again; Use deionized water wash at last 3～5 times,, obtain colourless or little yellow transparent liquid through the vacuum decompression drying;
(3) separation and purification: with the purified product acetic acid ethyl dissolution of step (2), the insolubles precipitation is separated out, removed solvent, obtain difunctionality isocyanuric acid acrylate or isocyanuric acid methacrylate monomer through underpressure distillation with centrifuging.
2. according to the preparation method of right 1 described difunctionality isocyanuric acid acrylate or isocyanuric acid methacrylate monomer, it is characterized in that: the mol ratio of described three (2-hydroxyethyl) isocyanuric acid esters and acrylic or methacrylic acid is 1: (3.0～3.3).
3. according to the preparation method of right 1 described difunctionality isocyanuric acid acrylate or isocyanuric acid methacrylate monomer, it is characterized in that: the time of described esterification dehydration is 5～6 hours.
4. according to the preparation method of right 1 described difunctionality isocyanuric acid acrylate or isocyanuric acid methacrylate monomer, it is characterized in that: described step (2) Na
2CO
3Solution quality concentration is 10%～15%; Saturated common salt water washing 2～3 times.
5. according to the preparation method of right 1 described difunctionality isocyanuric acid acrylate or isocyanuric acid methacrylate monomer, it is characterized in that: the insolubles of described step (3) is an isocyanuric acid mono acrylic ester insolubles.
6. the preparation method of three-functionality-degree isocyanuric acid acrylate or isocyanuric acid methacrylate monomer is characterized in that comprising the steps:
(1) the elementary product of monomer is synthetic: acrylic or methacrylic acid, three (2-hydroxyethyl) isocyanuric acid ester, band aqua, stopper and catalyzer are mixed, the oil bath heating, after the question response thing all dissolves, control reaction temperature is 100～120 ℃, carrying out the esterification dehydration generates until reactionless water, the cooling stopped reaction, decompression removes the band aqua, obtains containing the three-functionality-degree isocyanuric acid acrylate of triazine ring or the elementary product of isocyanuric acid methacrylate monomer; The mol ratio of described three (2-hydroxyethyl) isocyanuric acid esters and acrylic or methacrylic acid is 1: (5.5～8.0); Described catalyzer is a tosic acid, and consumption is 7.5%～10% of three (2-hydroxyethyl) isocyanuric acid ester quality; Described stopper is MEHQ or 2, and 6-Butylated Hydroxytoluene, consumption are 6%～8% of acrylic or methacrylic acid quality; Described band aqua is hexanaphthene and/or toluene, and consumption is 100%～140% of three (2-hydroxyethyl) isocyanuric acid ester quality;
(2) purify: step (1) reaction system is cooled to below 50 ℃, adds Na
2CO
3Solution is neutralized to PH=7.5～8, and is stirred well to no bubble generation, uses the saturated common salt water washing again, makes system be neutral; Spend dried up washing 3～5 times at last,, obtain white paste solid through the vacuum decompression drying;
(3) separation and purification: with mixed solvent (mass ratio is 1: (0.1～the 0.2)) dissolving of the purified product of step (2) with ethyl acetate and hexanaphthene, with centrifuging the insolubles precipitation is separated out, remove solvent through underpressure distillation, obtain three-functionality-degree isocyanuric acid acrylate or isocyanuric acid methacrylate monomer.
7. according to the preparation method of right 6 described three-functionality-degree isocyanuric acid acrylate or isocyanuric acid methacrylate monomer, it is characterized in that: the time of described esterification dehydration is 5～6 hours.
8. according to the preparation method of right 6 described three-functionality-degree isocyanuric acid acrylate or isocyanuric acid methacrylate monomer, it is characterized in that: described step (2) Na
2CO
3Solution quality concentration is 10%～15%; Saturated common salt water washing 2～3 times.
9. according to the preparation method of right 6 described three-functionality-degree isocyanuric acid acrylate or isocyanuric acid methacrylate monomer, it is characterized in that: the insolubles of described step (3) is isocyanuric acid mono acrylic ester and isocyanuric acid double methacrylate insolubles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101503273A CN102260221A (en) | 2011-06-07 | 2011-06-07 | Preparation method of isocyanurate acrylate or isocyanurate methacrylate monomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101503273A CN102260221A (en) | 2011-06-07 | 2011-06-07 | Preparation method of isocyanurate acrylate or isocyanurate methacrylate monomer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102260221A true CN102260221A (en) | 2011-11-30 |
Family
ID=45007087
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011101503273A Pending CN102260221A (en) | 2011-06-07 | 2011-06-07 | Preparation method of isocyanurate acrylate or isocyanurate methacrylate monomer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102260221A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104418815A (en) * | 2013-09-05 | 2015-03-18 | 安庆飞凯高分子材料有限公司 | Preparation method of tri(2-ethoxy) isocyanurate acrylate mixture |
| CN104557753A (en) * | 2014-12-17 | 2015-04-29 | 张家港康得新光电材料有限公司 | Preparation method of tri(2-ethoxyl) isocyanuric acid triacrylate |
| CN105102549A (en) * | 2013-03-29 | 2015-11-25 | Hoya株式会社 | Coating composition |
| CN105348208A (en) * | 2015-12-11 | 2016-02-24 | 安庆飞凯高分子材料有限公司 | Preparation method of tris(2-hydroxycyclohexyl) isocyanuric acid triacrylate |
| CN111116822A (en) * | 2019-12-31 | 2020-05-08 | 东莞市德聚胶接技术有限公司 | Acrylic resin composition |
| CN111875885A (en) * | 2020-08-03 | 2020-11-03 | 徐州海天石化有限公司 | Electret master batch special for melt-blown fabric and preparation method thereof |
| CN112480324A (en) * | 2019-09-11 | 2021-03-12 | 中国科学院福建物质结构研究所 | Raw material composition for preparing light-cured resin, light-cured resin prepared from raw material composition and application of light-cured resin |
| CN114539906A (en) * | 2021-12-31 | 2022-05-27 | 澳达树熊涂料(惠州)有限公司 | Anti-yellowing skin-feel matte top-coat paint and preparation method thereof |
| CN115260112A (en) * | 2022-06-27 | 2022-11-01 | 佳化化学科技发展（上海）有限公司 | Sexek derivative and preparation method and application thereof |
| CN115417968A (en) * | 2022-10-10 | 2022-12-02 | 世名(苏州)新材料研究院有限公司 | Hyperbranched polyurethane acrylate with isocyanuric acid as core and preparation method thereof |
| CN116463022A (en) * | 2023-04-19 | 2023-07-21 | 淄博市交通建设发展中心 | High weather-resistant water-based modified polyacrylic acid bridge concrete protective coating |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3821098A (en) * | 1971-08-17 | 1974-06-28 | Ciba Geigy Corp | Process for the curing of hydantoin containing acrylic acid ester derivatives with ionising rays |
-
2011
- 2011-06-07 CN CN2011101503273A patent/CN102260221A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3821098A (en) * | 1971-08-17 | 1974-06-28 | Ciba Geigy Corp | Process for the curing of hydantoin containing acrylic acid ester derivatives with ionising rays |
Non-Patent Citations (2)
| Title |
|---|
| 侯有军等: "三(2-羟乙基) 异氰脲酸丙烯酸酯特种单体的合成与表征", 《化工新型材料》 * |
| 侯有军等: "含三嗪环的异氰脲酸丙烯酸酯的合成及其紫外光固化性能", 《电渡与涂饰》 * |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105102549A (en) * | 2013-03-29 | 2015-11-25 | Hoya株式会社 | Coating composition |
| CN105102549B (en) * | 2013-03-29 | 2017-06-23 | Hoya株式会社 | Coating composition |
| US9873799B2 (en) | 2013-03-29 | 2018-01-23 | Hoya Corporation | Coating composition |
| CN104418815A (en) * | 2013-09-05 | 2015-03-18 | 安庆飞凯高分子材料有限公司 | Preparation method of tri(2-ethoxy) isocyanurate acrylate mixture |
| CN104418815B (en) * | 2013-09-05 | 2016-11-09 | 安庆飞凯高分子材料有限公司 | A kind of three (2-ethoxy) isocyanuric acid acrylate mixture preparation method |
| CN104557753A (en) * | 2014-12-17 | 2015-04-29 | 张家港康得新光电材料有限公司 | Preparation method of tri(2-ethoxyl) isocyanuric acid triacrylate |
| CN104557753B (en) * | 2014-12-17 | 2017-06-23 | 张家港康得新光电材料有限公司 | The preparation method of three (2 ethoxy) isocyanuric acid triacrylates |
| CN105348208A (en) * | 2015-12-11 | 2016-02-24 | 安庆飞凯高分子材料有限公司 | Preparation method of tris(2-hydroxycyclohexyl) isocyanuric acid triacrylate |
| CN112480324A (en) * | 2019-09-11 | 2021-03-12 | 中国科学院福建物质结构研究所 | Raw material composition for preparing light-cured resin, light-cured resin prepared from raw material composition and application of light-cured resin |
| CN111116822A (en) * | 2019-12-31 | 2020-05-08 | 东莞市德聚胶接技术有限公司 | Acrylic resin composition |
| CN111116822B (en) * | 2019-12-31 | 2021-04-16 | 东莞市德聚胶接技术有限公司 | Acrylic resin composition |
| CN111875885A (en) * | 2020-08-03 | 2020-11-03 | 徐州海天石化有限公司 | Electret master batch special for melt-blown fabric and preparation method thereof |
| CN111875885B (en) * | 2020-08-03 | 2022-10-14 | 徐州海天石化有限公司 | Electret master batch special for melt-blown fabric and preparation method thereof |
| CN114539906A (en) * | 2021-12-31 | 2022-05-27 | 澳达树熊涂料(惠州)有限公司 | Anti-yellowing skin-feel matte top-coat paint and preparation method thereof |
| CN114539906B (en) * | 2021-12-31 | 2023-03-21 | 澳达树熊涂料(惠州)有限公司 | Anti-yellowing skin-feel matte top-coat paint and preparation method thereof |
| CN115260112A (en) * | 2022-06-27 | 2022-11-01 | 佳化化学科技发展（上海）有限公司 | Sexek derivative and preparation method and application thereof |
| CN115417968A (en) * | 2022-10-10 | 2022-12-02 | 世名(苏州)新材料研究院有限公司 | Hyperbranched polyurethane acrylate with isocyanuric acid as core and preparation method thereof |
| CN115417968B (en) * | 2022-10-10 | 2023-11-10 | 世名(苏州)新材料研究院有限公司 | Hyperbranched polyurethane acrylate with isocyanuric acid as core and preparation method thereof |
| CN116463022A (en) * | 2023-04-19 | 2023-07-21 | 淄博市交通建设发展中心 | High weather-resistant water-based modified polyacrylic acid bridge concrete protective coating |
| CN116463022B (en) * | 2023-04-19 | 2024-01-30 | 淄博市交通建设发展中心 | High weather-resistant water-based modified polyacrylic acid bridge concrete protective coating |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102260221A (en) | Preparation method of isocyanurate acrylate or isocyanurate methacrylate monomer | |
| CN101397363B (en) | Water ultraviolet light curing epoxy acrylic ester grafted polyurethane and preparation method thereof | |
| CN102516326B (en) | Method for synthesizing tannin-based hyperbranched acrylic acid ester | |
| CN106977694B (en) | The cured urethane acrylate photosensitive resin of ultraviolet light and its preparation method and purposes | |
| Zhou et al. | Facile synthesis and characterization of urushiol analogues from tung oil via ultraviolet photocatalysis | |
| CN108863780B (en) | Application of immobilized heteropolyacid catalyst in preparation of fluorenyl acrylate | |
| CN102989506A (en) | Preparation method of novel immobilized ionic liquid catalyst | |
| CN101863763A (en) | Method for catalytically synthesizing isobornyl methacrylate by activated carbon supported stannic chloride | |
| CN106397368A (en) | Fatty alcohol-polyoxyethylene ether glycidyl ether and preparation method thereof | |
| WO2021135222A1 (en) | Multifunctional-epoxy-vegetable-oil-based uv-curable prepolymer, preparation method therefor and use thereof | |
| CN105001088B (en) | Method for preparing all-bio-based photocuring activated monomer and application of all-bio-based photocuring activated monomer | |
| CN103467298B (en) | Nutgalls acidic group photocuring reactive monomer and its preparation method and application | |
| CN107936846B (en) | Modified rosin resin and preparation method and application thereof | |
| CN105085324A (en) | Betaine type amphoteric ioncompound containing isocyanate groups and preparation method thereof | |
| CN111138290A (en) | Aromatic ring-containing benzophenone derivative and preparation method and application thereof | |
| CN111205203A (en) | Benzophenone derivative containing diphenyl carbamate group and preparation and application thereof | |
| CN101423602B (en) | Method for preparing ultraviolet crosslinking active multi-propenyl multi-arm star type prepolymer | |
| CN113735705B (en) | Method for catalyzing waste PET (polyethylene terephthalate) polyester to carry out methanol alcoholysis by polyion liquid | |
| CN112409297B (en) | Free radical-cation hybrid photo-curing monomer, preparation method thereof, radiation-curing coating and application | |
| CN110305327A (en) | Dendroid Eosin B-salt compounded of iodine visible light initiator and its preparation method and application | |
| CN107879910B (en) | Green synthesis process of 2, 4-dihydroxy benzophenone | |
| CN111217987A (en) | High-refractive-index UV resin, preparation method thereof and application of nano-imprinting | |
| CN101830836B (en) | Method for manufacturing pigment red 3BL condensation intermediate | |
| CN111057029B (en) | Fluorine-containing cationic polymerization monomer and synthesis and application thereof | |
| CN104418815A (en) | Preparation method of tri(2-ethoxy) isocyanurate acrylate mixture |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20111130 |